Epoxy vinyl ester resin anticorrosive paint and preparation method thereof

Abstract

The invention discloses an epoxy vinyl ester resin anticorrosive paint and a preparation method thereof, and the epoxy vinyl ester resin anticorrosive paint at least comprises the following raw materials by weight: 100-120 parts of epoxy vinyl ester resin; 0.75 to 0.8 part of a curing agent; 0.012 part to 0.015 part of a catalyst; 3 to 10 parts of styrene; 20 parts to 30 parts of ethyl orthosilicate; 30 to 36 parts of ethanol; 50 to 80 parts of normal hexane; and 5 to 15 parts of silicon dioxide aerogel. The epoxy vinyl ester resin anticorrosive paint has stronger corrosion resistance in an extreme environment, and the mechanical property and the thermal stability are further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-corrosion materials, and in particular to an epoxy vinyl ester resin anti-corrosion coating and a preparation method thereof. Background Art

[0002] The synthesis and performance optimization of new epoxy vinyl ester resins are research hotspots. With the continuous optimization of synthesis processes and the improvement of modification technologies, the research and development of new epoxy vinyl ester resins have achieved remarkable results. These resins have excellent properties such as high temperature stability, corrosion resistance, and high strength, meeting the needs of different fields for high-performance materials. Among them, the anti-corrosion performance of epoxy vinyl resin coatings is mainly achieved through the barrier effect of corrosive ions, water and oxygen, and is widely used in anti-corrosion coatings. However, existing epoxy vinyl resin coatings have the following defects: (1) The chemical corrosion resistance in extreme chemical environments still needs to be improved; (2) The mechanical strength and thermal stability of existing epoxy or polysiloxane anti-corrosion coatings are not ideal and need further improvement; (3) A large amount of organic solvents and additives need to be added during the preparation of the coatings, which is not conducive to environmental protection. There is an urgent need to develop solvent-free or low-volatile organic compound coatings. Summary of the Invention

[0003] The purpose of the present invention is to overcome the defects of existing epoxy vinyl ester resin coatings, such as poor corrosion resistance under extreme environments, weak mechanical strength and thermal stability, and insufficient environmental protection.

[0004] In order to achieve the above object, the present invention provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0005] Epoxy vinyl ester resin: 100 to 120 parts;

[0006] Curing agent: 0.75 to 0.8 parts;

[0007] Catalyst: 0.012 to 0.015 parts;

[0008] Styrene: 3 to 10 parts;

[0009] Ethyl orthosilicate: 20 to 30 parts;

[0010] Ethanol: 30 to 36 parts;

[0011] n-Hexane: 50 to 80 parts;

[0012] Silica aerogel: 5 to 15 parts.

[0013] Optionally, the curing agent is methyl ethyl ketone peroxide.

[0014] Optionally, the catalyst is cobalt naphthenate and / or N,N-dimethylaniline.

[0015] Optionally, the epoxy vinyl ester resin is VE-375.

[0016] The present invention also provides a method for preparing the epoxy vinyl ester resin anti-corrosion coating as described above, comprising the following steps:

[0017] S1, mixing ethyl orthosilicate, water, ethanol, and ammonium fluoride to obtain an aerogel, placing the aerogel into a mold, cooling to room temperature, aging, and baking in an oven. After baking, performing three solvent exchanges with n-hexane, and finally modifying the aerogel with a trimethylchlorosilane solution, followed by drying at room temperature and pressure to obtain a silica aerogel;

[0018] S2, grinding the silica aerogel, adding the ground silica aerogel to epoxy vinyl ester resin VE-375 and mechanically mixing to obtain a suspension, diluting the suspension with styrene, and then adding a mixture of methyl ethyl ketone peroxide and cobalt naphthenate / N,N-dimethylaniline, and mixing evenly to obtain the epoxy vinyl ester resin anti-corrosion coating.

[0019] Optionally, in S1, the three solvent exchanges refer to exchanges at 25°C, every 24 hours.

[0020] Optionally, in S1, the temperature of the oven is 75° C. and the baking time is 24 hours.

[0021] Optionally, in S1, the modification time is 24 hours.

[0022] Optionally, in S1, the aging time is 1 hour.

[0023] Optionally, in S1, the drying time is 5 hours.

[0024] Compared with the prior art, the beneficial effects of the present invention include at least:

[0025] The epoxy vinyl ester resin anti-corrosion coating of the present invention comprises silica aerogel synthesized by a one-step method, the aerogel is surface-treated with trimethylsilyl chloride, and the hydroxyl groups on the surface of the aerogel are replaced to generate methylsilyl groups, thereby reducing the surface energy and improving the contact angle from hydrophilic to hydrophobic, thereby making it hydrophobic. The coating also comprises an epoxy vinyl ester resin as a coating matrix, the molecular chain of which contains vinyl groups and can form a three-dimensional network structure through free radical polymerization and cross-linking with a curing agent, thereby imparting mechanical strength and chemical stability to the coating. The silica aerogel has enhanced compatibility with the epoxy vinyl ester resin, and its hydrophobic surface can reduce water absorption by the coating, further inhibiting corrosion electrochemical reactions. DETAILED DESCRIPTION

[0026] The technical solution of the present invention is further described below with reference to the embodiments.

[0027] Example 1

[0028] This embodiment provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0029] Epoxy vinyl ester resin VE-375: 100 parts;

[0030] Curing agent methyl ethyl ketone peroxide: 0.75 parts;

[0031] Catalyst mixture of cobalt naphthenate and / or N,N-dimethylaniline: 0.012 parts;

[0032] Styrene: 5 parts;

[0033] Ethyl orthosilicate: 20 parts;

[0034] Ethanol: 36 parts;

[0035] n-Hexane: 50 parts;

[0036] Silica aerogel: 5 parts.

[0037] S1, 20 parts of ethyl orthosilicate, 7 parts of water, 36 parts of ethanol, and 0.001 parts of ammonium fluoride are mixed to obtain an aerogel, the aerogel is placed in a mold, cooled to room temperature, aged for 1 hour, and then baked in an oven at 75°C for 24 hours. After baking, three solvent exchanges are performed with n-hexane (once every 24 hours, at 25°C). Finally, the aerogel is modified with a trimethylchlorosilane solution for 24 hours, and then dried at room temperature (21°C) and normal pressure for 5 hours to obtain a silica aerogel;

[0038] S2, grinding 5 parts of silica aerogel, adding the grounded silica aerogel to 100 parts of epoxy vinyl ester resin VE-375 and mechanically mixing for 2 hours to obtain a suspension, diluting the suspension with 5 parts of styrene, and then adding 0.75 parts of methyl ethyl ketone peroxide and 0.012 parts of a mixture of cobalt naphthenate / N,N-dimethylaniline, and mixing evenly to obtain the epoxy vinyl ester resin anti-corrosion coating.

[0039] Example 2

[0040] This embodiment provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0041] Epoxy vinyl ester resin VE-375: 100 parts;

[0042] Curing agent methyl ethyl ketone peroxide: 0.75 parts;

[0043] Catalyst mixture of cobalt naphthenate and / or N,N-dimethylaniline: 0.012 parts;

[0044] Styrene: 5 parts;

[0045] Ethyl orthosilicate: 20 parts;

[0046] Ethanol: 36 parts;

[0047] n-Hexane: 50 parts;

[0048] Silica aerogel: 10 parts.

[0049] S1, 20 parts of ethyl orthosilicate, 7 parts of water, 36 parts of ethanol, and 0.001 parts of ammonium fluoride are mixed to obtain an aerogel, the aerogel is placed in a mold, cooled to room temperature, aged for 1 hour, and then baked in an oven at 75°C for 24 hours. After baking, three solvent exchanges are performed with n-hexane (once every 24 hours, at 25°C). Finally, the aerogel is modified with a trimethylchlorosilane solution for 24 hours, and then dried at room temperature (21°C) and normal pressure for 5 hours to obtain a silica aerogel;

[0050] S2, grinding 10 parts of silica aerogel, adding the grounded silica aerogel to 100 parts of epoxy vinyl ester resin VE-375 and mechanically mixing for 2 hours to obtain a suspension, diluting the suspension with 5 parts of styrene, and then adding 0.75 parts of methyl ethyl ketone peroxide and 0.012 parts of a mixture of cobalt naphthenate / N,N-dimethylaniline, and mixing evenly to obtain the epoxy vinyl ester resin anti-corrosion coating.

[0051] Example 3

[0052] This embodiment provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0053] Epoxy vinyl ester resin VE-375: 100 parts;

[0054] Curing agent methyl ethyl ketone peroxide: 0.75 parts;

[0055] Catalyst mixture of cobalt naphthenate and / or N,N-dimethylaniline: 0.012 parts;

[0056] Styrene: 5 parts;

[0057] Ethyl orthosilicate: 20 parts;

[0058] Ethanol: 36 parts;

[0059] n-Hexane: 50 parts;

[0060] Silica aerogel: 15 parts.

[0061] S1, 20 parts of ethyl orthosilicate, 7 parts of water, 36 parts of ethanol, and 0.001 parts of ammonium fluoride are mixed to obtain an aerogel, the aerogel is placed in a mold, cooled to room temperature, aged for 1 hour, and then baked in an oven at 75°C for 24 hours. After baking, three solvent exchanges are performed with n-hexane (once every 24 hours, at 25°C). Finally, the aerogel is modified with a trimethylchlorosilane solution for 24 hours, and then dried at room temperature (21°C) and normal pressure for 5 hours to obtain a silica aerogel;

[0062] S2, grinding 15 parts of silica aerogel, adding the grounded silica aerogel to 100 parts of epoxy vinyl ester resin VE-375 and mechanically mixing for 2 hours to obtain a suspension, diluting the suspension with 5 parts of styrene, and then adding 0.75 parts of methyl ethyl ketone peroxide and 0.012 parts of a mixture of cobalt naphthenate / N,N-dimethylaniline, and mixing evenly to obtain the epoxy vinyl ester resin anti-corrosion coating.

[0063] Example 4

[0064] This embodiment provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0065] Epoxy vinyl ester resin VE-375: 120 parts;

[0066] Curing agent methyl ethyl ketone peroxide: 0.8 parts;

[0067] Catalyst mixture of cobalt naphthenate and / or N,N-dimethylaniline: 0.015 parts;

[0068] Styrene: 7 parts;

[0069] Ethyl orthosilicate: 20 parts;

[0070] Ethanol: 36 parts;

[0071] n-Hexane: 50 parts;

[0072] Silica aerogel: 15 parts.

[0073] S1, 20 parts of ethyl orthosilicate, 7 parts of water, 36 parts of ethanol, and 0.001 parts of ammonium fluoride are mixed to obtain an aerogel, the aerogel is placed in a mold, cooled to room temperature, aged for 1 hour, and then baked in an oven at 75°C for 24 hours. After baking, three solvent exchanges are performed with n-hexane (once every 24 hours, at 25°C). Finally, the aerogel is modified with a trimethylchlorosilane solution for 24 hours, and then dried at room temperature (21°C) and normal pressure for 5 hours to obtain a silica aerogel;

[0074] S2, grinding 15 parts of silica aerogel, adding the grounded silica aerogel to 120 parts of epoxy vinyl ester resin VE-375 and mechanically mixing for 2 hours to obtain a suspension, diluting the suspension with 7 parts of styrene, and then adding 0.8 parts of methyl ethyl ketone peroxide and 0.015 parts of a mixture of cobalt naphthenate / N,N-dimethylaniline, and mixing evenly to obtain the epoxy vinyl ester resin anti-corrosion coating.

[0075] Comparative Example 1

[0076] This comparative example provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0077] Epoxy vinyl ester resin VE-375: 100 parts;

[0078] Curing agent methyl ethyl ketone peroxide: 0.75 parts;

[0079] Catalyst mixture of cobalt naphthenate and / or N,N-dimethylaniline: 0.012 parts;

[0080] Styrene: 5 parts.

[0081] 100 parts of epoxy vinyl ester resin VE-375 were diluted with 5 parts of styrene, and then 0.75 parts of methyl ethyl ketone peroxide and 0.012 parts of a mixture of cobalt naphthenate / N,N-dimethylaniline were added and mixed evenly to obtain the epoxy vinyl ester resin anticorrosive coating.

[0082] Comparative Example 2

[0083] This comparative example provides an epoxy vinyl ester resin anti-corrosion coating, which comprises at least the following raw materials in parts by weight:

[0084] Epoxy vinyl ester resin VE-375: 100 parts;

[0085] Curing agent methyl ethyl ketone peroxide: 0.75 parts;

[0086] Catalyst mixture of cobalt naphthenate and / or N,N-dimethylaniline: 0.012 parts;

[0087] Styrene: 5 parts;

[0088] Ethyl orthosilicate: 20 parts;

[0089] Ethanol: 36 parts;

[0090] n-Hexane: 50 parts;

[0091] Silica aerogel: 5 parts.

[0092] S1, 20 parts of ethyl orthosilicate, 7 parts of water, 36 parts of ethanol, and 0.001 parts of ammonium fluoride are mixed to obtain an aerogel, the aerogel is placed in a mold, cooled to room temperature, aged for 1 hour, and then baked in an oven at 75°C for 24 hours. After baking, the solvent is exchanged three times with n-hexane (once every 24 hours, at 25°C), and then dried at room temperature (21°C) and normal pressure for 5 hours to obtain a silica aerogel;

[0093] S2. Grind 5 parts of silica aerogel, add the grounded silica aerogel to 100 parts of epoxy vinyl ester resin VE-375, and mechanically mix for 2 hours to obtain a suspension. Dilute the suspension with 5 parts of styrene, and then add 0.75 parts of methyl ethyl ketone peroxide and 0.012 parts of a mixture of cobalt naphthenate / N,N-dimethylaniline. Mix well to obtain the epoxy vinyl ester resin anti-corrosion coating.

[0094] The performance of the epoxy vinyl ester resin anticorrosive coatings prepared in the examples and comparative examples was tested, and the results are shown in Table 1.

[0095] Table 1 Product performance test of Examples 1 to 4 and Comparative Examples 1 to 2

[0096]

[0097]

[0098] As can be seen from Table 1, it can be seen from the Examples and Comparative Examples that the addition of silica aerogel to the epoxy vinyl ester resin anti-corrosion coating greatly improves the performance of the product. It can be seen from Comparative Example 2 and the Examples that the product performance is greatly improved after the aerogel is treated with trimethylsilyl chloride.

[0099] In summary, the epoxy vinyl ester resin anti-corrosion coating of the present invention includes silica aerogel synthesized by a one-step method, and the aerogel is surface-treated with trimethylsilyl chloride. The hydroxyl groups on the surface of the aerogel are replaced to generate methylsilyl groups, thereby reducing the surface energy and improving the contact angle from hydrophilic to hydrophobic to make it hydrophobic. The coating also includes an epoxy vinyl ester resin as a coating matrix, the molecular chain of which contains vinyl groups and can be cross-linked with a curing agent through free radical polymerization to form a three-dimensional network structure, thereby giving the coating mechanical strength and chemical stability. The compatibility of the silica aerogel with the epoxy vinyl ester resin is enhanced, and its hydrophobic surface can reduce water absorption of the coating, further inhibiting corrosion electrochemical reactions.

[0100] Although the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description is not intended to limit the present invention. After reading the above description, various modifications and substitutions of the present invention will become apparent to those skilled in the art. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. An epoxy vinyl ester resin anticorrosive coating, characterized in that: Calculated by weight, it contains at least the following raw materials: Epoxy vinyl ester resin: 100 to 120 parts; Curing agent: 0.75 to 0.8 parts; Catalyst: 0.012 to 0.015 parts; Styrene: 3 to 10 parts; Ethyl orthosilicate: 20 to 30 parts; Ethanol: 30 to 36 parts; n-Hexane: 50 to 80 parts; Silica aerogel: 5 to 15 parts.

2. The epoxy vinyl ester resin anticorrosive coating according to claim 1, wherein The curing agent is methyl ethyl ketone peroxide.

3. The epoxy vinyl ester resin anticorrosive coating according to claim 1, wherein The catalyst is cobalt naphthenate and / or N,N-dimethylaniline.

4. The epoxy vinyl ester resin anticorrosive coating according to claim 1, wherein The epoxy vinyl ester resin is VE-375.

5. A method for preparing the epoxy vinyl ester resin anticorrosive coating according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1, mixing ethyl orthosilicate, water, ethanol, and ammonium fluoride to obtain an aerogel, placing the aerogel into a mold, cooling to room temperature, aging, and baking in an oven. After baking, performing three solvent exchanges with n-hexane, and finally modifying the aerogel with a trimethylchlorosilane solution, followed by drying at room temperature and pressure to obtain a silica aerogel; S2, grinding the silica aerogel, adding the ground silica aerogel to epoxy vinyl ester resin VE-375 and mechanically mixing to obtain a suspension, diluting the suspension with styrene, and then adding a mixture of methyl ethyl ketone peroxide and cobalt naphthenate / N,N-dimethylaniline, and mixing evenly to obtain the epoxy vinyl ester resin anti-corrosion coating.

6. The preparation method according to claim 5, wherein In S1, the three solvent exchanges refer to exchanges at 25°C, every 24 hours.

7. The preparation method according to claim 5, wherein In S1, the temperature of the oven is 75°C and the baking time is 24h.

8. The preparation method according to claim 5, wherein In S1, the modification time is 24 h.

9. The preparation method according to claim 5, wherein In S1, the aging time is 1 h.

10. The preparation method according to claim 5, characterized in that In S1, the drying time is 5 h.

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